Method of metallizing azoic dyeings



United States METHOD OF METALLIZIN G AZOIC DYEINGS Clemens Streck,Loudonville, N. Y., assignor to General Aniline & Film Corporation, NewYork, N. Y., a corporation of Delaware No Drawing. Application August 2,1956 Serial No. 601,658

12 Claims. (Cl. 842) This invention relates to an" improved process ofmetallizing azoic dyeings.

The fiber may be impregnated with a coupling component and passed into asolution which contains an active diazo either in the form of freshlyprepared diazo or as a Fast Color Salt solution under conditionssuitable for coupling. pounds which, except for a few diazos which aresufficiently stable per se, are diazo compounds which are stabilized bysalt formation such as with certain metallic salts, e. g. MgCl ZnCl SnCletc., arylsulfonic acids such as naphthalene-1,5-disulfonic acid andnaphthalene- 1,3,6-trisulfonic acid, and also borofluoric acid. v

One of the outstanding advantages of azoic dyeings is their fastness incontrast to that of the usual azo dyes. The fastness of azoicdyeings hasrecently been improved by metallizing, i. efby treating the previouslydyed fibers with various metallizing agents such as Cu, Co, Cr, Ni andthe like. In the art as now practiced, it is necessary to dye thefibrous material with an azoic dye devoid of solubilizing groupsfollowed by an after treatment with a metallizing agent. The metallizingstep represents an extra step and also requires at least about 20minutes. To overcome this, satisfactory metallization of azoic dyeingsis achieved by incorporating the metallizing agent in the soaping bathas taught in my United States patent (Serial No. 316,305).

I have found that fibrous material dyed with an azoic dye, free fromsolubilizing groups and capable of conversion into a complex metalcompound, is endowed with improved light-, washand chlorine-fastnessproperties and of improved shades by carrying out azoic color formationin the presence of the metallizing agent. In other words, themetallizing agent may be dissolved in a naphtholating bath, the fibrousmaterial impregnated with this bath, usually followed by drying, and theimpreg- Fast Color Salts are diazo comnated fiber padded or printed withan active diazo which includes afreshly prepared diazo or a diazostabilized as a Fast Color Salt, and then metallizing with hot water orpreferably with steam. Thetemperature and moisture conditions of the hotwater or steam, are sufficiently drastic to yield complete metallizationtogether with color development, even when exposed to steam for lessthan 1 I minute; Theflimportant advantage ofthis improved method. isthat a satisfactorymetallized product is. obtained without anyadditional operations other than the usual dyeing steps. By this,procedure, economical dyeings are obtained as contrasted with thepresent method of after metallizing which requires additional steps,over and above the dyeing steps, i. "e., treatment with the metallizingagent and-heating; Iv lhedi'azosafid the coupling components employed inaccordance with this. invention are those which producedyes-'havinghydroxy groups ortho to the azo linkage or groups which areconvertible into hydroxy groups such as lower alkoxy, i. e.methoxy,'ethoxy, propoxy and butoxy,

"which are fr'eefrom-solubiliz'ing {group s such as sulfonic I andcarboxylic acids.

2,867,494 Patented .1m... 5.1 4 5 4-benzamido-2,5-dimethoxyaniline2,5-dimethoxy-4-(p-nitrobenzeneazo) aniline 4-cyano-2,5-dimethoxyaniline5-diethylsulfa myl-o-anisidine 4-phenylamino-o-anisidine5-n-butylsulfamyl-o-hydroxyaniline- 5-amino-6-hydroxyquinoline I In thecase where the coupling component contains'the o,o'-dihydroxyconfiguration, the above may be used, as also those free from theo-hydroxy and alkoxy configura: tion, e. g. p-chloroaniline,p-anisidine, benzidine.

The coupling components may, in general, be selected from the NaphtholAS compounds which are arylides of 2-hydroxy-3-naphthoic acid andrelated S-hydroxy carboxylic acid derivatives, acetoacetarylides andrelated fl-oxocarboxylic acid arylides and pyrazolones. However, othercompounds may be employed which are capable of coupling to yield acomponent having the required metallizable group in ortho position tothe azo linkage. Thus, in addition to the coupling componentsspecificially set forth in the examples, the following couplingcomponents may bev employed; Z-naphthol, 3- hydroxy-2-.(2,5-dimethoxy)naphthanilide, 3-l1ydroxy-2- (N-naphthyl)naphthamide, 3 hydroxy 2(4'-chloro) naphthanilide, 3 hydroxy 2 (N-2-methoxy-3-diben'zo'-furyl)naphthamide, 3 hydroxyanthraquinone 2 carboX-o-toluidide,2-hydroxy-3-dibenzofurancarboxylic acid arylides such as 2 hydroxy 3dibenz'ofuran;(2'.,5;'di

methoxy)carboxanilide, bis(acetoacet)benzidide, bis(acetoacet)tolidide,acylacetarylides such as acetoacet-4-chloro-2,5-dimethoxyanilide, 3hydroxy 2 carbazolecarboxylic acid arylides such asIi-hydroxy-Z-carbazole-(p+ chloro)carboxyanilide, terephthaloylbisacetoacet (3'- chloro-2',4'-dimethoxy)-anilide, pyrazolones, such aslphenyl-3-methyl-5-pyrazolone, 3-h'ydroxy 2 naphthoic acid arylides,3-hydroxy-2-anthroic acid arylides, 2-hydroXy-4-nitroaniline 2-naphthol,o-hydroXy-anilineresorcinol, 2-hydroxy-S-nitroaniline resorcinol; ,In...the case of the couplers in the last two examples listed, wherein theo-hydroxyazo linkage is present in the coupler per se, any ordinarydiazo compounds may be employed, such asm-chloro-aniline,o'-nitroahiline, l-aminoanthraquinone .and2-amino-4,4'-dichlorodiphenyloxide. Other similar couples may beemployed, "such as those listed in German Patent 618,748;

The process of the present inventionljijs 'appltcable'to cotton, andregenerated cellulose, which can be dyed by the process of-thepresentinvention.-v V i In practicing the present invention 0.1 to 10 parts ofa naphthol-type coupling component isdissolved 1 to parts of watercontaining 0.1 to 5 parts of caustic baa 100% basis. To this solution isadded 0.1 to 10 parts of ametal salt whichwaspreviously, dissolved andcoordinated Iii order that han-1am -"salt maintain "solubility under thealkaline condition of a naphthol solution any one of the usual andcommercially available chelating agents is used in-'--conjunction withthe metal salt.

The chelating agent is capable of forming a complex with the metallizingagent and acts as a coordinating agent to maintain the soluble metalsalt such as copper, cobalt or nickel in the form of chloride, nitrate,sulfate, acetate, and the like. Examples of such chelating agents(coordinating agents) include triethanolamine, tartaric acid, glycine,dimethylglycine, glycollic acid, aspartic acid, glutamic acid, lacticacid, a-hydroxybutyric acid and the like. The amount of chelatingagentemployed isthat necessary to .maintain solubility of the metal saltunder alkaline conditions and may range from 50-250 parts by weightofchelating agent per 100 parts by weight of metal salt. Theoreticallythese chelating agents are added in approximately molecularly equivalentamounts to that of the metallizing compound, but in actual practice theaforementioned proportions may be departed from to obtain the mostdesirable results depending on conditions of dyeing and type ofcoordinating agent employed. Approximately one mole copper-to two of dyealso gives satisfactory improvement.

As stated above the metallizing compounds are salts and hydroxides of ametal selected from the group consisting of copper (cupic), nickel andcobalt. They are employed in the form of chlorides, sulphates, acetates,formates, nitrates, and the like. Those compounds are preferred whichare relatively water soluble or dispersible. The. amount of metal saltor metal hydroxide, to be employed will usually depend on the degree ofmetallizing desired. Molar ratios are necessary for completemetallization but the amount may range from about a fraction of an.equivalent to an excess of one equivalent of metal per equivalent ofdye.

The strength of dyeing is generally. of the order of about 0.0 5..l%.based on theweight of. the fiber, depending on the shade desired, about0.1-8%. being the usual range to give sufiicient and satisfactorydyeing.

The diazo may be supplied by an amine freshly diazotiz ed by. treatmentwith nitrite in the customary manner, or the diazo may be a stabilizeddiazo, i. e., in the form of diazonium chloride or sulfate, or intheform of the diazo stabilized as a double salt, i. .e., as a zincchloride, boron trifluoride, tin chloride, naphthalenedisulfonic acid,etc.

As illustrative examples of Fast Color Salts the following areillustrative:

Fast Blue .Salt BN CH3 Fast "Blue Salt 2BN GQHIC ONH N'-N-Cl.%ZnCh CaHvFast Red Salt BN N=NO;

OsN SOsH Fast Red Salt TRN 01Q-N=N'Oa8 Y CHa' aH Fast Black Salt K 4Fast Bordeaux Salt BD Variamin'e Blue Salt BD Fast Red Salt RL' Fast RedSalt FR weight of the fibrous. material employed unless otherwiseindicated.

Example I A naphthol c-ouplin'g solution was made up by dissolving 3grams of B-hydroxy-Z-naphthoic acid 'anilide in 6 cc. of isopropylalcohol, 1 /2 cc. of caustic soda 34 B. andy2 cc. of water.

A metal containing solution was made by dissolving 25 grams of tartaricacid in 120 cc. of water. To this soluti on was added 25 grams of copperchloride, 75 cc. of caustic soda 34 B. and made up to 250 cc. withwater.

The naphthol solution was poured into 50 cc. of water containing 2 /2cc. of caustic soda 34 B., and 10 cc. of the aqueous alkaline copperchloride solution, and made up to 133 cc. by the addition of water.

A gram sample of cotton was padded with the naphthol coupling and metalcontaining solution and dried. It was then padded with a solution madeup by dissolving 6 grams of the zinc chloride salt of tetrazotizeddianisidine, 0.5 cc. of commercial wetting agent, which is a 40% cc.solution of a fatty alcohol-ethylene oxide condensation product, and 2'cc. of 50% aqueous acetic acid and water added to make up to a volumeof 133 cc. After padding, the material was exposed to steam atatmospheric pressure for 20-60 seconds.

A dyeing was obtained which was somewhat redder than a similar dyeingmade without metallization with considerably betterlight-, washandchlorine-fastness.

Example 11 Example I was repeated with the exception that in the metalcontaining solution copper chloride was replaced by 25 grams of cobaltchloride. The dyeing obtained was. somewhat redder than a similar dyeingwithout metallization with considerably betterlight-, washandchl'orine-fastness;

Example Ill Example I was repeated with the. exception that the tartaricacid inthe metal containing solution was replaced by 25 gramsofglycine.A dyeing .was obtained which has considerable light-,. washandchlorine-fastnes's.

Example IV Example I was again repeated withthe exceptionthat the3-hydroxy-2-naphthoic acid anilidewas replaced by 2 grams of1-phenyl-3-methylpyrazolone. A. dyeing having excellent light-, washandchlorine-fastness properties was obtained.

Example V Example I was again repeated with the exception that the3-hydroxy-2-naphthoic acid anilide was replaced by an equivalent amountof S-hydroXy-Z-naphthoic acid toluidide, and the zinc chloride salt oftetrazotized dianisidine was replaced by an equivalent amount of thezinc chloride salt of diazotized 4-benz amido-2,5-dimethoxyaniline. Adyeing was obtained having excellent light-,' washand chlorine-fastnessproperties.

Example Vl Example VII Example I was again repeated with the exceptionthat the 3-hydroxy-2-naphthoic acid anilide was replaced by anequivalent amount of"2-hydroxybenzeneazo-4-resorcinol, and the zincchloride salt of tetrazotized di-anisidine was replaced by an equivalentamount of the zinc chloride .double salt of the diazoofS-chloro-o-anisidine. A dyeing was obtained havingexcellent lightfastness.

Example VIII Example I wasagain repeated with the exception that in themetal containing solution copper chloride was replaced by an equivalentamount of nickel chloride. A dyeing of excellent light and washfastnesswas obtained.

Example IX Example I was again repeated with the exception that in themetal containing solution the copper chloride was replaced by anequivalent amount of copper sulfate. A dyeing of excellent lightand washfastness was obtained.

Example X Example I was again repeated with the exception that the3-hydroxy-2-naphthoic acid was replaced by 1.5 grams of ,B-naphthol. Adeep navy shade was obtained of good light-, washand chlorine-fastness.

Example XI 3 grams of 3-hydroxy-2-naphthoic acid anilide and 1 grain ofbis(acetoacet)o-to1idide were dissolved in 100 cc. boiling watercontaining 4 /2 cc. caustic soda 34 B. To this solution, cooled to toabout 140 F., was added cc. of the copper chloride solution of ExampleI.

Cotton was padded with this solution and dried.

It was then padded with a solution of 8.5 grams of zinc chloride doublesalt of tetrazotized dianisidine, 0.5 cc. of a 40% fattyalcohol-ethylene oxide condensation product, 3 cc. of 50% aqueous aceticacid solution and water added to make up to a volume of 133 cc.,followed by treatment with steam for 25 seconds. A deep jet black wasobtained of improved light fastness.

Example XII Example I was again repeated with the exception that afterthe padding with the Fast Color Salt, the cotton was given a 30 secondrinse in boiling water.

While the metallizing efiect was not quite as good as the dyeing ofExample I, i. e. exposed to steam, it was considerably better in lightfastness than a dyeing which had not been metallized.

Example XIII 2.2 grams of 4-(o-hydroxyphenylazo)resorcinol weredissolved in 6 cc.'ethyl'alcoho1, 1% cc. caustic 34.B. and 2 cc. ofwater.

A metal-containing solution was made up containing: 147 grams of coppersulfate, 683 cc. of water, cc. of triethanolamine and 60 grams of drycaustic.

The naphthol solution was poured into a solution containing 50 cc.water, 2 /2 cc. caustic soda 34 B., and 10 cc. of the metallizingsolution, and made up to 133 cc. with water.

Cotton was padded with this solution and dried. It was then padded withFast Color Salt and treated with steam, as in Example I. A deep brown ofgood light fastness was obtained.

Example XIV A solution was made up as follows:

soda

-An additional metal-containing paste was made up as follows:

1 II A Parts Copper sulfate 14.7 Triethanolamine 11.0 I and II' weremixed together.

A padding bath was made up as follows:

Acetic acid 50% 2 Water up to 1 gal. 1

The cotton was padded with this solution and steamed for 25 seconds. Adeep navy, fast to light, dyeing was obtained.

Therm'etallizing compounds, i. e. metal salts, can be incorporated intothe Rapidogen printing pastes and solutions,-, and on development inacidified steam the color is developed and metallizing occurssimultaneously.

The diazoamino compounds are the usual ones,.free from solubilizinggroups in the diazo portion, containing at least one solubilizing groupin the amino portion, and in addition, containing a hydroxy or a loweralkoxy substituent ortho to the diazo group, except in the rare instancewhere the coupling components may contain an o,o'-dihydroxy-type azoconfiguration.

The following examples illustrate the foregoing embodirnent:

Example XV Two solutions were made up as follows:

Solution The copper solution contained 147 parts copper sul- 7. fate,683 parts water, 110 parts triethanolamine and 60 parts dry caustic.

17 grams of A and 20 grams of B were. thickened with starch tragacanth.

Cotton was printed with printing pastesA and B, steamed in acid steam ina normal manner for 2 minutes, rinsed and dried.

The dyeing from solution A was slightly redder, and had much betterlight fastness than a similar unmetallized dyeing- The dyeing fromsolution B was slightly less red than A, slightly stronger and showed asimilar fastness to v light.

Example XVI A printing paste was made upas follows:

4 grams Rapidogen mix (cresidine diazotized and stabilized withsarcosine+3-hydroxy-3 -nitroQ-naphthanilide), 4 cc. ethylene glycolmonoethyl ether, 24 cc. water, 3 cc. sodium hydroxide 34 B., 5 cc.copper solution, as em ployed in Example I, gum tragacanth to printingthickness.

Cotton cloth was printed 'with'this paste and developed for 2 minutes inacidified steam. A yellower coloration, having excellent lightfastness,was produced than in an unmetallized dyeing.

Example XVII Example XVI was repeated with the exception that theRapidogen mix was replaced by an equivalent amount of a Rapidogenconsisting of dianisidine tetrazotized and stabilized with methyltaurine+phenyl methylpyrazolone, and employing 10 cc. of the coppersolution of Example XV. In this case a tan coloration was produced whichhad excellent light fastness properties.

Example XVIII 1. The process of metallizing azoic dyeings whichcomprises impregnating a fibrous material selected from the classconsisting of cotton and regenerated cellulose with an alkaline solutionof an azoic coupling component, a coordinating agent selected from theclass consisting of aliphatic aminoand hydroxy-carboxylic acids, and ametallizing compound ofthe group consisting of soluble and dispersiblesalts of copper, cobalt, and nickel, and then treating the impregnatedfiber with a diazo solution, in which the diazo is free fromsolubilizing groups, and simultaneously dyeing and metallizing in situby treatment.atelevated temperatures with an aqueous medium having a pHof not more than 7, the said azoic coupling component and the said diazoyielding an o, o-dihydroxy configuration in the final dyestufi.

2. The processv according to claim 1 wherein the metallizing compound iscopper chloride.

3. The process according to claim lizing compound is cobalt chloride.

4. The process according to claim 1 wherein the metallizing compound isnickel chloride;

5. The process according to claim 1 wherein the metallizing compound iscopper sulfate.

' 6. The process according to claim 1 wherein the metallizing compoundis cobalt sulfate.

7. An alkaline azoic coupling bath for impregnating fibrous materialsselected from the class consisting of cotton and regenerated celluloseprior to dyeing with a diazo compound, free from solubilizing groups,which converts to a complex metal compound comprising an alkalinesolution of an azoic coupling component, a coordinating agent selectedfrom the group consisting of aliphatic aminoandhydroxy-carboxylic acids,and a metallizing compound of the group consisting of salts andhydroxides of copper, cobalt, and nickel, the said azoic couplingcomponent yielding upon coupling with the said diazo compound adyestuflcontaining an o,o'-dihydroxy configuration.

8. A bath for impregnation of fibrous materials according to claim 7wherein the metallizing compound is copper chloride.

9.A bath for impregnation of fibrous materials according to claim 7wherein the metallizing compound is cobalt chloride.

10. A bath for impregnation of fibrous materials according to claim 7wherein the metallizing compound is nickel chloride.

11.'A bath for impregnation of fibrous materials according to claim'7wherein the metallizing compound is copper sulfate.

12. A bath for impregnation of fibrous materials according to claim 7wherein the metallizing compound is cobalt sulfate.

1 wherein the metal- References Cited in the tile of this patent FOREIGNPATENTS 502,144 Great Britain Mar. 7, 1939 531,470 Great Britain Jan. 6,1941

1. THE PROCESS OF METALLIZING AZOIC DYEINGS WHICH COMPRISES IMPREGNATINGA FIBROUS MATERIAL SELECTED FROM THE CLASS CONSISTING OF COTTON ANDREGENERATED CELLULOSE WITH AN ALKALINE SOLUTION OF AN AZOIC COUPLINGCOMPONENT, A COORDINATING AGENT SELECTED FROM THE CLASS CONSISTING OFALIPHATIC AMINO- AND HYDROXY-CARBOXYLIC ACIDS, AND A METALLIZINGCOMPOUND OF THE GROUP CONSISTING OF SOLUBLE AND DISPERSIBLE SALTS OFCOPPER, COBALT, AND NICKEL, AND THEN TREATING THE IMPREGNATED FIBER WITHA DIAZO SOLUTION, IN WHICH THE DIAZO IS FREE FROM SOLUBILIZING GROUPS,AND SIMULTANEOUSLY DYEING AND METALLIZING IN SITU BY TREATMENT ATELEVATED TEMPERATURES WITH AN AQUEOUS MEDIUM HAVING A PH OF NOT MORETHAN 7, THE SAID AZOIC COUPLING COMPONENT AND THE SAID DIAZO YIELDING ANO, O-DIHYDROXY CONFIGURATION IN THE FINAL DYESTUFF.